Search Results (23)

This research explores the enhancement of bio-oil quality through upgrading with the magnetic bimetallic oxide (CuO-Fe₃O₄) catalysts supported on activated rice straw biochar (AcB). These catalysts were employed in a supercritical ethanol-based upgrading process. Various characterization techniques, including elemental analysis, Fourier transform infrared (FTIR), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), were utilized to characterize the prepared catalysts. This study revealed significant improvements in the physical characteristics and chemical composition of the bio-oil, with an increase in the heating value (HHV) from 21.3 to 32.1 MJ/kg. Esterification and transesterification were identified as key reactions contributing to this improvement. Notably, the pH of bio-oil increased from 4.3 (raw bio-oil) to 5.63 (after upgrading), signifying reduced acidity. The analysis of the bio-oil’s chemical composition highlighted a decrease in oxygen content and an increase in carbon and hydrogen content. At the optimum conditions, the application of supercritical ethanol proved to be an efficient method for enhancing the bio-oil’s properties. A crucial transformation occurred during the upgrading process and more than 90% of carboxylic acids were converted into esters, primarily ethyl acetate at the optimal conditions. This study has demonstrated the effective enhancement of raw bio-oil from rice straw through the utilization of carbon-based bimetallic oxide catalysts in a supercritical upgrading procedure. Full article

The global trend towards net-zero carbon emissions from burning fuels in combustion engines alerts us to the alternative role of biodiesel. The manufacturing cost of biodiesel hinders the fast development of various types of biofuels. Feedstock cost is one of the major determining factors of biodiesel cost and thus the extent of its competitiveness in the fuel market with other available alternative fuels or fossil fuels. Some low-cost feedstocks such as high-acid oil, which is produced from the acidifying processes of soybean soapstock, frequently contain high contents of free fatty acids (FFAs) and water. Hence, those feedstocks cannot be used to produce biodiesel through strong alkaline catalyst transesterification on an industrial scale. In contrast, the water can be converted to hydroxyl radicals to enhance the formation of esters from the dissociation of the FFA in a supercritical reacting tank. Hence, cheap high-acid oils containing high amounts of water and FFAs were used to produce biodiesel through a supercritical transesterification reaction system. The engine emission characteristics of using the biodiesel produced in this study were analyzed and compared with those of commercial biodiesel and super-low sulfur diesel (SLSD). A naturally aspirated, direct-injection, four-stroke, four-cylinder marine diesel engine associated with an eddy-current dynamometer was used to carry out the engine emission measurement. In comparison with super-low sulfur diesel (SLSD), the biodiesel had lower CO₂ and CO emissions and black smoke opacity but higher emissions of O₂ and NO_x. The higher engine speed caused lower emissions of O₂ and NO_x but higher CO₂ emissions. The supercritical-transesterification biodiesel appeared to be a competitive alternative fuel to fossil diesel. Full article

Biodiesel production through transesterification results in a large quantity of crude glycerol as a byproduct, the utilization of which is technically and economically challenging. Because of the ability to efficiently process wet feedstocks, supercritical water gasification (SCWG) is utilized in this study to convert crude glycerol into hydrogen-rich syngas. A significant challenge addressed through this study is the decomposition routes of different heterogeneous components of crude glycerol during SCWG. Pure glycerol, methanol and oleic acid were investigated for SCWG as the model compounds of crude glycerol. SCWG of model compounds at temperature, pressure, feedstock concentration and reaction time of 500 °C, 23–25 MPa, 10 wt% and 1 h, respectively, revealed methanol to exhibit the highest H₂ yield of 7.7 mmol/g, followed by pure glycerol (4.4 mmol/g) and oleic acid (1.1 mmol/g). The effects of feedstock concentration from 30 wt% to 10 wt% increased H₂ yield from all model compounds. Response surface methodology (RSM) was used to develop a response curve to visualize the interactive behavior and develop model equations for the prediction of H₂-rich gas yields as a function of the composition of model compounds in the crude glycerol mixture. Predictive models showed a good agreement with experimental results, demonstrating high accuracy and robustness of the model. These findings demonstrated a strong potential of crude glycerol for SCWG to generate H₂-rich syngas. Full article

The effect of temperature was studied on the synthesis of fatty acid alkyl esters by means of transesterification of waste beef tallow using ethanol and, iso-butanol and 1-butanol at supercritical conditions. These alcohols are proposed for the synthesis of biodiesel in order to improve the cold flow properties of alkyl esters. Alcohol–beef tallow mixtures were fed to a high-pressure high-temperature autoclave at a constant molar ratio of 45:1. Reactions were carried out in the ranges of 310–390 °C and 310–420 °C for ethanol and iso-butanol, respectively; meanwhile, synthesis using 1-butanol was assessed only at 360 °C. After separation of fatty acid alkyl esters, these samples were characterized by nuclear magnetic resonance (NMR) and gas chromatography coupled to mass spectrometry (GC-MS) to quantify yields, chemical composition, and molecular weight. Results indicated that yields enhanced as temperature increased; the maximum yields for fatty acid ethyl esters (FAEEs) were attained at 360 °C, and for fatty acid butyl esters (FABEs) were achieved at 375 °C; beyond these conditions, the alkyl ester yields reached equilibrium. Concerning the physicochemical properties of biodiesel, the predicted cetane number and cloud point were enhanced compared to those of fatty acid methyl esters. Full article

Biodiesel was produced via transesterification reaction catalyzed by acids, bases, enzymes or supercritical fluids. The catalysis was homogeneous or heterogeneous and the process could be carried out in batch or using a continuous flow process. Microreactors allowed us to obtain better control of the experimental variables, such as temperature, pressure and flow rate, carrying out the reactions in safe conditions, avoiding exothermic and dangerous processes. The synthetic methodologies in continuous flow, combined with other technologies as microwave irradiation or ultrasounds, led to complete automation of the process with an increase in efficiency, also applicable on an industrial scale. Full article

Biodiesel, comprising mono alkyl fatty acid esters or methyl ethyl esters, is an encouraging option to fossil fuels or diesel produced from petroleum; it has comparable characteristics and its use has the potential to diminish carbon dioxide production and greenhouse gas emissions. Manufactured from recyclable and sustainable feedstocks, e.g., oils originating from vegetation, biodiesel has biodegradable properties and has no toxic impact on ecosystems. The evolution of biodiesel has been precipitated by the continuing environmental damage created by the deployment of fossil fuels. Biodiesel is predominantly synthesised via transesterification and esterification procedures. These involve a number of key constituents, i.e., the feedstock and catalytic agent, the proportion of methanol to oil, the circumstances of the reaction and the product segregation and purification processes. Elements that influence the yield and standard of the obtained biodiesel encompass the form and quantity of the feedstock and reaction catalyst, the proportion of alcohol to feedstock, the temperature of the reaction, and its duration. Contemporary research has evaluated the output of biodiesel reactors in terms of energy production and timely biodiesel manufacture. In order to synthesise biodiesel for industrial use efficaciously, it is essential to acknowledge the technological advances that have significant potential in this sector. The current paper therefore offers a review of contemporary progress, feedstock categorisation, and catalytic agents for the manufacture of biodiesel and production reactors, together with modernised processing techniques. The production reactor, form of catalyst, methods of synthesis, and feedstock standards are additionally subjects of discourse so as to detail a comprehensive setting pertaining to the chemical process. Numerous studies are ongoing in order to develop increasingly efficacious techniques for biodiesel manufacture; these acknowledge the use of solid catalytic agents and non-catalytic supercritical events. This review appraises the contemporary situation with respect to biodiesel production in a range of contexts. The spectrum of techniques for the efficacious manufacture of biodiesel encompasses production catalysed by homogeneous or heterogeneous enzymes or promoted by microwave or ultrasonic technologies. A description of the difficulties to be surmounted going forward in the sector is presented. Full article

This work investigates the non-catalyzed supercritical methanol (SCM) process for continuous biodiesel production. The lab-scale setup was designed and used for biodiesel production in the temperature range of 520–650 K and 83–380 bar with an oil-to-methanol molar ratio ranging from 1:5 to 1:45. The experiments were performed in the coiled plug flow tubular reactor. The volumetric flow rate of the methanol/oil ranged from 0.1–10 mL/min. This work examines a new reactor technology involving preheating and pre-mixing of the methanol/oil mixture to reduce setup cost and increase biodiesel yield under the same reaction conditions. Work performed showed that FAME’s yield increased rapidly with temperature and pressure above the methanol critical points (i.e., 513 K and 79.5 bar). The best methyl-ester yield using this reaction technology was 91% at 590 K temperature and 351 bars with an oil-to-methanol ratio of 39 and a 15-min residence time. Furthermore, the kinetics of the free catalyst transesterification process was studied in supercritical methanol under different reaction conditions. Full article

Biodiesels and biolubricants are synthetic esters produced mainly via a transesterification of other esters from bio-based resources, such as plant-based oils or animal fats. Microwave heating has been used to enhance transesterification reaction by converting an electrical energy into a radiation, becoming part of the internal energy acquired by reactant molecules. This method leads to major energy savings and reduces the reaction time by at least 60% compared to a conventional heating via conduction and convection. However, the application of microwave heating technology alone still suffers from non-homogeneous electromagnetic field distribution, thermally unstable rising temperatures, and insufficient depth of microwave penetration, which reduces the mass transfer efficiency. The strategy of integrating multiple technologies for biodiesel and biolubricant production has gained a great deal of interest in applied chemistry. This review presents an advanced transesterification process that combines microwave heating with other technologies, namely an acoustic cavitation, a vacuum, ionic solvent, and a supercritical/subcritical approach to solve the limitations of the stand-alone microwave-assisted transesterification. The combined technologies allow for the improvement in the overall product yield and energy efficiency. This review provides insights into the broader prospects of microwave heating in the production of bio-based products. Full article

Dependence on fossil fuels for meeting the growing energy demand is damaging the world’s environment. There is a dire need to look for alternative fuels that are less potent to greenhouse gas emissions. Biofuels offer several advantages with less harmful effects on the environment. Biodiesel is synthesized from the organic wastes produced extensively like edible, non-edible, microbial, and waste oils. This study reviews the feasibility of the state-of-the-art feedstocks for sustainable biodiesel synthesis such as availability, and capacity to cover a significant proportion of fossil fuels. Biodiesel synthesized from oil crops, vegetable oils, and animal fats are the potential renewable carbon-neutral substitute to petroleum fuels. This study concludes that waste oils with higher oil content including waste cooking oil, waste palm oil, and algal oil are the most favorable feedstocks. The comparison of biodiesel production and parametric analysis is done critically, which is necessary to come up with the most appropriate feedstock for biodiesel synthesis. Since the critical comparison of feedstocks along with oil extraction and biodiesel production technologies has never been done before, this will help to direct future researchers to use more sustainable feedstocks for biodiesel synthesis. This study concluded that the use of third-generation feedstocks (wastes) is the most appropriate way for sustainable biodiesel production. The use of innovative costless oil extraction technologies including supercritical and microwave-assisted transesterification method is recommended for oil extraction. Full article

The constant increase in greenhouse gases in the environment is forcing people to look for different ways to reduce such pollution. One of these ways is the use of biodiesel for road transport. Conventional biodiesel production involves the catalytic triglyceride transesterification process. When using homogeneous two-stage catalysis, it is difficult to purify the resulting product from the by-products formed, and the catalysts cannot be reused. In the case of heterogeneous catalysis, the process costs are increased due to separation and regeneration of the catalysts. To solve these problems of catalytic synthesis, a noncatalytic process has been recently studied that which takes place under supercritical conditions for an alcohol or other acyl receptor. In such biodiesel production, fatty feedstocks and alcohols are used as raw materials, with the synthesis taking place at supercritical conditions for alcohol, i.e., high temperature and pressure, thus making the process quite simple. This paper reviews the results obtained from biodiesel synthesis using a noncatalytic supercritical process for transesterification using both alcohols and carboxylate esters of low molecular weight, evaluating the optimal conditions for these processes and biofuel stability at high temperatures. Full article

According to the International Air Transport Agency (IATA), the aviation industry causes 2% of GHG emissions. As a result, goals such as improving aircraft efficiency by 1.5% per year and achieving carbon-neutral growth by 2020 were established. In this circumstance, fuels produced from biomass seem to be a promising route. There are many routes available to convert biomass into renewable fuels such as pyrolysis, hydroprocessing, transesterification, hydrothermal processes, and steam reforming. In this study, one reports a review of hydrothermal technologies. This review reports recent information about hydrothermal processes using water in sub- and supercritical states. This article introduces some concepts of the hydrothermal processes, advantages, and different types of feedstock adopted. The parameters which have an influence on hydrothermal processes such as temperature, pressure, particle size, catalyst, biomass/water ratio, and reaction time are illuminated. Water characteristics in sub- and supercritical conditions are discussed as a highly reactive medium to increase the affinity for the extraction of value-added compounds. Additionally, this review splits and details the reaction schemes that take place under hydrothermal conditions. Finally, it introduces recent research and development (R&D) trends in the hydrothermal process of fatty acids and triglycerides. Full article

Avocado oil is prized for its high nutritional value due to the substantial amounts of triglycerides (TGs) and unsaturated fatty acids (FAs) present. While avocado oil is traditionally extracted from mature fruit flesh, alternative sources such as avocado seed oil have recently increased in popularity. Unfortunately, sufficient evidence is not available to support the claimed health benefit and safe use of such oils. To address potential quality issues and identify possible adulteration, authenticated avocado oils extracted from the fruit peel, pulp and seed by supercritical fluid extraction (SFE), as well as commercial avocado pulp and seed oils sold in US market were analyzed for TGs and FAs in the present study. Characterization and quantification of TGs were conducted using UHPLC/ESI-MS. Thirteen TGs containing saturated and unsaturated fatty acids in avocado oils were unambiguously identified. Compared to traditional analytical methods, which are based only on the relative areas of chromatographic peaks neglecting the differences in the relative response of individual TG, our method improved the quantification of TGs by using the reference standards whenever possible or the reference standards with the same equivalent carbon number (ECN). To verify the precision and accuracy of the UHPLC/ESI-MS method, the hydrolysis and transesterification products of avocado oil were analyzed for fatty acid methyl esters using a GC/MS method. The concentrations of individual FA were calculated, and the results agreed with the UHPLC/ESI-MS method. Although chemical profiles of avocado oils from pulp and peel are very similar, a significant difference was observed for the seed oil. Principal component analysis (PCA) based on TG and FA compositional data allowed correct identification of individual avocado oil and detection of possible adulteration. Full article

Marine cyanobacteria represent a large untapped source of functional glycolipids enriched with polyunsaturated fatty acids (PUFAs) for human health. However, advanced methods for scalable isolation of diverse species containing high-purity PUFA-rich glycolipids will have to be developed and their possible pharmaceutical and nutraceutical functions identified. This paper introduces a novel solid matrix-supported supercritical CO₂ extraction method for scalable isolation of the PUFA γ-linolenic acid (GLA)-enriched glycolipids from the cyanobacterium Arthrospira (Spirulina) platensis, which has been the most widely used among microalgae in the nutraceutical and pharmaceutical industries. Of various porous materials studied, diatomite was the best to facilitate extraction of GLA-rich glycolipids, resulting in an extraction efficiency of 98%. Gamma-linolenic acid made up 35% of total fatty acids (TFAs) in the extracts, which was considerably greater than that obtained with ethanol (26%), Bligh and Dyer (24%), and in situ transesterification (24%) methods, respectively. Lipidomics analysis revealed that GLA was exclusively associated with galactolipids. Pharmaceutical functions of GLA-rich galactolipids were investigated on a zebrafish caudal fin regeneration model. The results suggested that GLA extracted from A. platensis possessed anti-oxidative, anti-inflammatory, and anti-allergic activities, which acted in a concerted manner to promote post-injury regeneration of zebrafish. Full article

In earlier work (Silva et al., 2016; Soh et al., 2014a; Soh et al., 2015), the supercritical CO₂ transesterification of triolein to methyl-oleate using Nafion solid-acid catalyst and large methanol/triolein molar feed ratios was carried out. Herein, these ratios are adjusted (from 50–550) to evaluate the yield of fatty acid methyl esters in batch laboratory reactors as temperature is varied from 80–95 °C and pressure is varied from 8.0–9.65 MPa. Also, to better understand the effect of varying these operating parameters, batch reactor simulations using the Soave-Redlich-Kwong Equation of State (RK-ASPEN EOS) in ASPEN PLUS are carried-out. A single-reaction kinetic model is used and phase equilibrium is computed as the reactions proceed. Experimental data are compared with these results. Full article

In response to existing global focus on improved biodiesel production methods via highly efficient catalyst-free high temperature and high pressure technologies, this study considered the comparative study of catalyst-free technologies for biodiesel production as an important research area. In this study, therefore, catalyst-free integrated subcritical lipid hydrolysis and supercritical esterification and catalyst-free one step supercritical transesterification processes for biodiesel production have been evaluated via undertaking straight forward comparative energetic and environmental assessments. Energetic comparisons were undertaken after heat integration was performed since energy reduction has favourable effects on the environmental performance of chemical processes. The study confirmed that both processes are capable of producing biodiesel of high purity with catalyst-free integrated subcritical lipid hydrolysis and supercritical esterification characterised by a greater energy cost than catalyst-free one step supercritical transesterification processes for an equivalent biodiesel productivity potential. It was demonstrated that a one-step supercritical transesterification for biodiesel production presents an energetically more favourable catalyst-free biodiesel production pathway compared to the integrated subcritical lipid hydrolysis and supercritical esterification biodiesel production process. The one-step supercritical transesterification for biodiesel production was also shown to present an improved environmental performance compared to the integrated subcritical lipid hydrolysis and supercritical esterification biodiesel production process. This is because of the higher potential environment impact calculated for the integrated subcritical lipid hydrolysis and supercritical esterification compared to the potential environment impact calculated for the supercritical transesterification process, when all material and energy flows are considered. Finally the major contributors to the environmental outcomes of both processes were also clearly elucidated. Full article